Reactive dyes, processes for their preparation and their use

ABSTRACT

Reactive dyes of formula (1)                    
     wherein 
     b is the number 1 or 2, 
     A is the radical of formula (2) or (3)                    
     D 1 , D 2 , R 1 , R 2 , X 1 , Y, l, m and n are as defined in the specification, are especially suitable for dyeing cotton and wool and yield dyeings having good all round properties.

This is a continuation of application Ser. No. 09/704,354, filed on Nov. 2, 2000, now U.S. Pat. No. 6,323,327.

The present invention relates to novel reactive dyes, to processes for their preparation and to their use in the dyeing or printing of textile fibre materials.

The practice of dyeing using reactive dyes has recently led to higher demands being made of the quality of the dyeings and the profitability of the dyeing process. As a result, there is still a need for novel reactive dyes having improved properties, especially in respect of their application.

Dyeing nowadays requires reactive dyes that have sufficient substantivity and at the same time have good ease of washing off of unfixed dye. They should also have a good tinctorial yield and high reactivity, the objective being to provide especially dyeings having high degrees of fixing. The known dyes do not satisfy these requirements in all properties.

The problem underlying the present invention is accordingly to find, for the dyeing and printing of fibre materials, novel improved reactive dyes that possess the qualities characterised above to a high degree. The novel dyes should especially be distinguished by high fixing yields and high fibre-dye binding stability; it should also be possible for dye that is not fixed to the fibre to be washed off easily. The dyes should also yield dyeings having good allround properties, for example fastness to light and to wetting.

It has been shown that the problem posed is largely solved by the novel dyes defined below.

The present invention accordingly relates to reactive dyes of formula (1)

wherein

b is the number 1 or 2,

A is a radical of formula (2) or (3)

D₁ is a radical of formula

 or the radical of an azo dye when b is the number 1 or the radical of an aromatic tetraazo component when b is the number 2,

D₂ is the radical of a diazo component, of the benzene or naphthalene series,

R₁ and R₂ are each independently of the other hydrogen or C₁-C₄alkyl,

(R₃)₀₋₂ denotes from 0 to 2 substituents selected from the group C₁-C₄alkyl, C₁-C₄alkoxy, halogen and sulfo,

X₁ is fluorine or chlorine,

Y is vinyl or a radical —CH₂—CH₂—U and U is a group removable under alkaline conditions,

l is the number 2, 3, 4, 5 or 6, and

m and n are each independently of the other the number 0 or 1, wherein

when A is a radical of formula (3) and D₁ is the radical of an azo dye, at least one of the radicals D₁ and D₂ contains a fibre-reactive radical of formula (2) with the proviso that A is a radical of formula (2) when D₁ is the radical of an aromatic tetraazo component, and A is a radical of formula (3) when D₁ is a radical of formula (4).

The radicals R₁ and R₂ in a reactive dye of formula (1) are as alkyl radicals straight-chain or branched. The following radicals may be mentioned by way of example: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl.

R₁, and R₂ are preferably hydrogen or methyl and especially hydrogen.

R₃ as halogen is, for example, fluorine, chlorine or bromine, preferably chlorine or bromine and especially chlorine.

R₃ as C₁-C₄alkyl is, for example, methyl, ethyl, n- or iso-propyl or n-, sec-, tert- or iso-butyl, preferably methyl or ethyl and especially methyl.

As C₁-C₄alkoxy for R₃ there come into consideration, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and isobutoxy, preferably methoxy and ethoxy and especially methoxy.

R₃ preferably denotes one or two sulfo radicals, especially one sulfo radical.

As a group U removable under alkaline conditions there come into consideration, for example, —Cl, —Br, —F, —OSO₃H, —SSO₃H, —OCO—CH₃, —OPO₃H₂, —OCO—C₆H₅, —OSO₂—C₁-C₄alkyl and —OSO₂—N(C₁-C₄alkyl)₂. U is preferably a group of formula —Cl, —OSO₃H, —SSO₃H, —OCO—CH₃, —OCO—C₆H₅ or —OPO₃H₂, especially —Cl or —OSO₃H.

Examples of suitable radicals Y are accordingly vinyl, β-bromo- or β-chloro-ethyl, β-acetoxy-ethyl, β-benzoyloxyethyl, β-phosphatoethyl, β-sulfatoethyl and β-thiosulfatoethyl. Y is preferably vinyl, β-chloroethyl or β-sulfatoethyl.

X₁ is preferably chlorine.

l preferably denotes the number 3 or 4 and especially 3.

m preferably denotes the number 1.

The reactive dyes of formula (1) according to the invention preferably correspond to a dye of formula (1a)

wherein

D₁ is the radical of an azo dye when b is the number 1 or the radical of an aromatic tetraazo component when b is the number 2, and

R₁, Y, b, l and m have the definitions and preferred meanings given above.

In a further preferred embodiment, the reactive dyes of formula (1) according to the invention correspond to a dye of formula (1b)

wherein

D₂, R₁, R₂, X₁, Y, l, m and n have the definitions and preferred meanings given above.

Suitable substituents of D₁ as a radical of an azo dye and of D₂ include the substituents customary for azo dyes. The following may be mentioned by way of example: C₁-C₄alkyl, which is to be understood as being methyl, ethyl, n- or iso-propyl, and n-, iso-, sec- or tert-butyl; C₁-C₄alkoxy, which is to be understood as being methoxy, ethoxy, n- or iso-propoxy and n-, iso-, sec- or tert-butoxy; hydroxy-C₁-C₄alkoxy; phenoxy; C₂-C₆alkanoylamino unsubstituted or substituted in the alkyl moiety by hydroxy or by C₁-C₄alkoxy, e.g. acetyl-amino, hydroxyacetylamino, methoxyacetylamino or propionylamino; benzoylamino unsubstituted or substituted in the phenyl moiety by hydroxy, sulfo, halogen, C₁-C₄alkyl or by C₁-C₄alkoxy; C₁-C₆alkoxycarbonylamino unsubstituted or substituted in the alkyl moiety by hydroxy, C₁-C₄alkyl or by C₁-C₄alkoxy; phenoxycarbonylamino unsubstituted or substituted in the phenyl moiety by hydroxy, C₁-C₄alkyl or by C₁-C₄alkoxy; amino; N-C₁-C₄alkyl- or N,N-di-C₁-C₄alkyl-amino unsubstituted or substituted in the alkyl moiety by hydroxy, C₁-C₄alkoxy, carboxy, cyano, halogen, sulfo, sulfato, phenyl or by sulfophenyl, e.g. methylamino, ethyl-amino, N,N-dimethylamino, N,N-diethylamino, β-cyanoethylamino, β-hydroxyethylamino, N,N-di-β-hydroxyethylamino, β-sulfoethylamino, γ-sulfo-n-propylamino, β-sulfatoethylamino, N-ethyl-N-(3-sulfobenzyl)-amino, N-(β-sulfoethyl)-N-benzylamino; cyclohexylamino; N-phenylamino or N-C₁-C₄alkyl-N-phenylamino unsubstituted or substituted in the phenyl moiety by nitro, C₁-C₄alkyl, C₁-C₄alkoxy, carboxy, halogen or by sulfo; C₁-C₄alkoxycarbonyl, e.g. methoxy- or ethoxy-carbonyl; trifluoromethyl; nitro; cyano; halogen, which is to be understood generally as being, for example, fluorine, bromine or especially chlorine; ureido; hydroxy; carboxy; sulfo; sulfomethyl; carbamoyl; carbamido; sulfamoyl; N-phenylsulfamoyl or N-C₁-C₄alkyl-N-phenylsulfamoyl unsubstituted or substituted in the phenyl moiety by sulfo or by carboxy; methyl- or ethyl-sulfonyl.

Suitable substituents of D₁ as a radical of an azo dye and of D₂ also include fibre-reactive radicals.

Fibre-reactive radicals are to be understood as being those which are capable of reacting with the hydroxy groups of the cellulose, with the amino, carboxy, hydroxy and thiol groups in wool and silk or with the amino and possibly carboxy groups of synthetic polyamides to form covalent chemical bonds. The fibre-reactive radicals are generally bonded to the dye radical directly or via a bridge member. Suitable fibre-reactive radicals are, for example, those having at least one removable substituent at an aliphatic, aromatic or heterocyclic radical or those wherein the mentioned radicals contain a radical suitable for reaction with the fibre material, for example a vinyl radical.

A fibre-reactive radical present in D₁ as a radical of an azo dye and in D₂ preferably corresponds to formula (2a), (5a), (5b), (5c), (5d), (5e) or (5f)

wherein

Hal is chlorine or bromine;

X₂ is halogen, carboxypyridin-1-yl or 3-carbamoylpyridin-1-yl;

T₁ has independently the same definitions as X₂, or is a non-fibre-reactive substituent or a fibre-reactive radical of formula (6a), (6b), (6c), (6d), (6e) or (6f)

 wherein

R₄ and R₇ each independently of the other have the same definitions and preferred meanings as R₁ and R₂,

R₅ is hydrogen, C₁-C₄alkyl unsubstituted or substituted by hydroxy, sulfo, sulfato, carboxy or by cyano, or a radical

R₆ is hydrogen, hydroxy, sulfo, sulfato, carboxy, cyano, halogen, C₁-C₄alkoxycarbonyl,

C₁-C₄alkanoyloxy, carbamoyl or a group —SO₂—Y,

alk and alk₁ are each independently of the other linear or branched C₁-C₆alkylene,

arylene is a phenylene or naphthylene radical unsubstituted or substituted by sulfo, carboxy, C₁-C₄alkyl, C₁-C₄alkoxy or by halogen,

Q is a radical —O—or —NR₇—wherein R₇ is as defined above,

W is a group —SO₂—NR₅—, —CONR₅— or —NR₅CO— wherein R₅ is as defined above,

Y has the definitions and preferred meanings given above,

Y₁ is a group —CH(Hal)—CH₂—Hal or —C(Hal)═CH₂ and Hal is chlorine or bromine, and

I has the definitions and preferred meanings given above,

k is the number 2, 3, 4, 5 or 6 and r is the number 0 or 1; and

X₃ is halogen or C₁-C₄alkylsulfonyl;

X4 is halogen or C₁-C₄alkyl and

T₂ is hydrogen, cyano or halogen.

R₅ is preferably hydrogen or C₁-C₄alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl and especially hydrogen, methyl or ethyl. R₅ is especially hydrogen.

R₆ is preferably hydrogen.

k is preferably the number 2 or 3 and especially 2.

For a non-fibre-reactive substituent T₁ there come into consideration, for example, the following radicals:

hydroxy;

C₁-C₄alkoxy, for example methoxy, ethoxy, n- or iso-propoxy, n-, sec-, iso- or tert-butoxy, especially methoxy or ethoxy; the mentioned radicals are unsubstituted or substituted in the alkyl moiety, for example by C₁-C₄alkoxy, hydroxy, sulfo or by carboxy;

C₁-C₄alkylthio, for example methylthio, ethylthio, n- or iso-propylthio or n-butylthio; the mentioned radicals are unsubstituted or substituted in the alkyl moiety, e.g. by C₁-C₄alkoxy, hydroxy, sulfo or by carboxy;

amino;

N-mono- or N,N-di-C₁-C₆alkylamino, preferably N-mono- or N,N-di-C₁-C₄alkylamino; the mentioned radicals are unsubstituted, uninterrupted or interrupted in the alkyl moiety by oxygen or substituted in the alkyl moiety, e.g. by C₂-C₄alkanoylamino, C₁-C₄alkoxy, hydroxy, sulfo, sulfato, carboxy, cyano, carbamoyl or by sulfamoyl; examples that may be mentioned include N-methylamino, N-ethylamino, N-propylamino, N,N-dimethylamino and N,N-diethylamino, N-β-hydroxyethylamino, N,N-di-β-hydroxyethylamino, N-2-(β-hydroxyethoxy)ethylamino, N-2-[2-(β-hydroxyethoxy)ethoxy]ethylamino, N-β-sulfatoethylamino, N-β-sulfoethylamino, N-carboxymethylamino, N-β-carboxy-ethylamino, N-α,β-dicarboxy-ethyl-amino, N-α,γdicarboxypropylamino and N-ethyl-N-β-hydroxyethylamino or N-methyl-N-β-hydroxyethylamino;

C₅-C₇cycloalkylamino, for example cyclohexylamino, which includes both the unsubstituted radicals and the radicals substituted in the cycloalkyl ring, e.g. by C₁-C₄alkyl, especially methyl, or by carboxyl;

phenylamino or N-C₁-C₄alkyl-N-phenylamino, which includes both the unsubstituted radicals and the radicals substituted in the phenyl ring, e.g. by C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄-alkanoylamino, carboxy, carbamoyl, sulfo or by halogen, for example 2-, 3- or 4-chloro-phenylamino, 2-, 3- or 4-methylphenylamino, 2-, 3- or 4-methoxyphenylamino, 2-, 3- or 4-sulfophenylamino, disulfophenylamino or 2-, 3- or 4-carboxyphenyl-amino;

naphthylamino unsubstituted or substituted in the naphthyl ring, e.g. by sulfo, preferably the radicals substituted by from 1 to 3 sulfo groups, for example 1- or 2-naphthylamino, 1-sulfo-2-naphthylamino, 1,5-disulfo-2-naphthylamino or 4,8-disulfo-2-naphthylamino; or benzylamino unsubstituted or substituted in the phenyl moiety, e.g. by C₁-C₄alkyl, C₁-C₄-alkoxy, carboxy, sulfo or by halogen.

As a non-fibre-reactive radical, T₁ is preferably C₁-C₄alkoxy, C₁-C₄alkylthio, hydroxy, amino, N-mono- or N,N-di-C₁-C₄alkylamino unsubstituted or substituted in the alkyl moiety by hydroxy, sulfato or by sulfo, morpholino, or phenylamino or N—C₁-C₄alkyl-N-phenylamino (wherein the alkyl is unsubstituted or substituted by hydroxy, sulfo or by sulfato) each unsubstituted or substituted in the phenyl ring by sulfo, carboxy, acetylamino, chlorine, methyl or by methoxy, or naphthylamino unsubstituted or substituted by from 1 to 3 sulfo groups.

Especially preferred non-fibre-reactive radicals T₁ are amino, N-methylamino, N-ethylamino, N-β-hydroxyethylamino, N-methyl-N-β-hydroxyethylamino, N-ethyl-N-β-hydroxyethylamino, N,N-di-β-hydroxyethylamino, morpholino, 2-, 3- or 4-carboxyphenylamino, 2-, 3- or 4-sulfophenylamino or N—-C₁-C₄alkyl-N-phenylamino.

X₂ is preferably halogen, for example fluorine, chlorine or bromine and especially chlorine or fluorine.

T₂, X₃ and X₄ as halogen are, for example, fluorine, chlorine or bromine, especially chlorine or fluorine.

X₃ as C₁-C₄alkylsulfonyl is, for example, ethylsulfonyl or methylsulfonyl and especially methylsulfonyl.

X₄ as C₁-C₄alkyl is, for example, methyl , ethyl, n- or iso-propyl, n-, iso- or tert-butyl and especially methyl.

X₃ and X₄ are preferably each independently of the other chlorine or fluorine.

T₂ is preferably cyano or chlorine.

Hal is preferably bromine.

alk and alk₁ are each independently of the other, for example, a methylene, ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene or 1,6-hexylene radical or a branched isomer thereof.

alk and alk₁ are preferably each independently of the other a C₁-C₄alkylene radical and especially an ethylene radical or propylene radical.

arylene is preferably a 1,3- or 1,4-phenylene radical unsubstituted or substituted, for example, by sulfo, methyl, methoxy or by carboxy, and especially an unsubstituted 1,3- or 1,4-phenylene radical.

Q is preferably —NH— or —O— and especially —O—.

W is preferably a group of formula —CONH— or —NHCO—, especially a group of formula —CONH—.

r is preferably the number 0.

The reactive radicals of formulae (6a) to (6f) are preferably those wherein W is a group of formula —CONH—, R₅, R₆ and R₇ are each hydrogen, Q is a radical —O— or —NH—, alk and alk₁ are each independently of the other ethylene or propylene, arylene is phenylene unsubstituted or substituted by methyl, methoxy, carboxy or by sulfo, Y is vinyl or β-sulfatoethyl, Y₁ is —CHBr—CH₂Br or —CBr═CH₂ and r is the number 0.

A fibre-reactive radical present in D₁ as the radical of an azo dye and in D₂ corresponds especially to formula (2a), (5a), (5b), (5c), (5d) or (5e) wherein Y is vinyl, β-chloroethyl or β-sulfatoethyl, Hal is bromine, R₄ is hydrogen, I is the number 3 or 4, k is the number 2 or 3, X₂ is chlorine or fluorine, T₁ is C₁-C₄alkoxy, C₁-C₄alkylthio, hydroxy, amino, N-mono- or N,N-di-C₁-C₄alkylamino unsubstituted or substituted in the alkyl moiety by hydroxy, sulfato or by sulfo, morpholino, or phenylamino or N—C₁-C₄alkyl-N-phenylamino (wherein the alkyl is unsubstituted or substituted by hydroxy, sulfo or by sulfato) each unsubstituted or substituted in the phenyl ring by sulfo, carboxy, acetylamino, chlorine, methyl or by methoxy, or naphthylamino unsubstituted or substituted by from 1 to 3 sulfo groups, or is a fibre-reactive radical of formula (6a′), (6b′), (6c′), (6d′) or (6f′)

—NH—(CH₂)₂₋₃—SO₂Y  (6a′),

—NH—(CH₂)₂₋₃—O—(CH₂)₂₋₃—SO₂Y  (6b′),

 especially (6c′) or (6d′), wherein

Y is as defined above, and

Y₁ is a group —CH(Br)—CH₂—Br or —C(Br)═CH₂.

In the case of the radicals of formulae (6a′) and (6b′), Y is preferably β-chloroethyl. In the case of the radicals of formulae (6c′) and (6d′), Y is preferably vinyl or β-sulfatoethyl.

D₁ as the radical of an azo dye preferably corresponds to formula

wherein

R₈ is hydrogen or C₁-C₄alkyl,

X₅ is fluorine or chlorine, and

G is a monoazo or disazo radical of formula (8) or (9)

D—N═N—(M—N═N)_(u)—K—  (8)

or

—D—N═N—(M—N═N)_(u)—K  (9),

 wherein

D is the radical of a diazo component, of the benzene or naphthalene series,

M is the radical of a central component, of the benzene or naphthalene series,

K is the radical of a coupling component, of the benzene, naphthalene, pyrazolone, 6-hydroxypyrid-2-one or acetoacetic acid arylamide series, and

u is a number 0 or 1,

wherein D, M and K may carry substituents customary for azo dyes.

The expression “substituents customary for azo dyes” is intended to include both fibre-reactive and non-fibre-reactive substituents, for example the substituents mentioned above for D₁ and D₂.

As non-fibre-reactive substituents for D, M and K in G there come into consideration especially C₁-C₄alkyl or C₁-C₄alkoxy unsubstituted or further substituted by hydroxy, sulfo or by sulfato, halogen, carboxy, sulfo, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, amino, ureido, hydroxy, sulfomethyl, C₂-C₄alkanoylamino, benzoylamino unsubstituted or substituted in the phenyl ring by C₁-C₄alkyl, C₁-C₄alkoxy, halogen or by sulfo, or phenyl unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxy or by sulfo.

The monoazo or disazo radicals of formula (8) or (9) preferably contain at least one sulfo group.

Preferred monoazo or disazo radicals G are the radicals of formulae (10a), (10b), (10c), (10d), (10e), (10f), (10g), (10h), (10i), (10j), (10k), (10l), (10m), (10n), (10o) and (10p)

wherein

(R₉)₀₋₃ denotes from 0 to 3 identical or different substituents from the group C₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxy and sulfo, (R₁₀)₀₋₃ denotes from 0 to 3 identical or different substituents from the group halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C₁-C₄alkyl, C₁-C₄alkoxy unsubstituted or substituted by hydroxy, sulfato or by C₁-C₄alkoxy, amino, C₂-C₄alkanoylamino, ureido, hydroxy, carboxy, sulfomethyl, C₁-C₄alkylsulfonylamino and sulfo, preferably from 0 to 2 identical or different substituents from the group C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoyl-amino ureido, sulfo and C₁-C₄alkoxy unsubstituted or substituted in the alkyl moiety by hydroxy or by sulfato, and

Z₁, where present, is a radical of formula (2a), (5a), (5b), (5c), (5d) or (5e), preferably (2a), (5a) or (5b) and especially (5a), the mentioned radicals having the definitions and preferred meanings given above,

wherein R₁₁ is C₂-C₄alkanoyl or benzoyl,

wherein (R₁₂)₀₋₃ denotes from 0 to 3 identical or different substituents from the group C₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxy and sulfo,

wherein R₁₃ and R₁₅ are each independently of the other hydrogen, C₁-C₄alkyl or phenyl, and R₁₄ is hydrogen, cyano, carbamoyl or sulfomethyl,

 wherein

(R₉)₀₋₃,(R₁₀)₀₋₃ and (R₁₂)₀₋₃ are each as defined above,

(R₁₆)₀₋₃ and (R₁₇)₀₋₃ each independently of the other denote from 0 to 3 identical or different substituents from the group C₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxy and sulfo, and Z₁ has the definitions and preferred meanings given above.

As C₁-C₄alkyl for R₈, R₉, R₁₀, R₁₂, R₁₃, R₁₅, R₁₆ and R₁₇, each independently of the others, there come into consideration e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl and isobutyl, preferably methyl and ethyl. As C₁-C₄alkyl, R₈ is especially methyl and R₁₅ is especially ethyl.

As C₁-C₄alkoxy for R₉, R₁₀, R₁₂, R₁₆ and R₁₇, each independently of the others, there come into consideration e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and isobutoxy, preferably methoxy and ethoxy and especially methoxy. R₁₀ is unsubstituted or substituted in the alkyl moiety by hydroxy or by sulfato.

As halogen for R₉, R₁₀, R₁₂, R₁₆ and R₁₇, each independently of the other, there come into consideration e.g. fluorine, chlorine and bromine, preferably chlorine and bromine and especially chlorine.

As C₂-C₄alkanoylamino for R₁₀ there come into consideration e.g. acetylamino and propionyl-amino, especially acetylamino.

R₁₁ is e.g. acetyl or propionyl.

(R₉)₀₋₃ in the disazo radicals of formulae (10n) and (10p) preferably denotes from 0 to 3 sulfo groups.

The numbers on the naphthyl rings of the radicals of formulae (10a), (10b), (10c), (10d), (10e), (10g) and (10h) indicate the possible bonding positions.

Especially preferred monoazo or disazo radicals G are the radicals of formulae (10a), (10b), (10d), (10e), (10f), (10k) and (10m), especially (10a), (10b), (10d) and (10e).

R₈ is preferably hydrogen or methyl and especially hydrogen.

X₅ is preferably chlorine.

D₁ as the radical of an azo dye of formula (7) preferably corresponds to formula (7a)

wherein X_(5,) R₈ and G have the definitions and preferred meanings given above.

In a further preferred embodiment of the present invention, D₁ as the radical of an azo dye corresponds to a monoazo radical of formula (11) or (12)

D*—N═N—K**—  (11)

or

—D*—N═N—K*  (12),

preferably of formula (11), wherein D* is the radical of a diazo component, of the benzene or naphthalene series, K* is the radical of a coupling component, of the benzene, naphthalene, pyrazolone, 6-hydroxypyrid-2-one or acetoacetic acid arylamide series, and K** is the radical of a coupling component, of the benzene, naphthalene or pyrazolone series, wherein D*, K* and K** may carry substituents customary for azo dyes.

As non-fibre-reactive substituents for D*, K* and K** there come into consideration preferably C₁-C₄alkyl or C₁-C₄alkoxy unsubstituted or further substituted by hydroxy, C₁-C₄alkoxy, sulfo or by sulfato, halogen, carboxy, sulfo, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, amino, ureido, hydroxy, sulfomethyl, C₂-C₄alkanoylamino, C₁-C₄alkylsulfonyl-amino, benzoylamino unsubstituted or substituted in the phenyl ring by C₁-C₄alkyl, C₁-C₄-alkoxy, halogen or by sulfo, or phenyl unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄-alkoxy, halogen, carboxy or by sulfo.

As fibre-reactive substituents for D*, K* and K** there come into consideration preferably the radicals of formulae (2a), (5a), (5b), (5c), (5d) and (5e), preferably (2a), (5a) and (5b) and especially (5a), the mentioned radicals having the definitions and preferred meanings given above.

The monoazo radicals of formula (11) or (12) preferably contain at least one sulfo group.

Preferred monoazo radicals D₁ of formula (11) correspond to the radicals of the above-mentioned formulae (10a), (10b), (10d), (10e), (10f) and (10l) or to the radicals of formulae (11a), (11b), (11c), (11d), (11e) and (11f)

wherein (R₉)₀₋₃ and Z₁ have the definitions and preferred meanings given above.

Especially preferred monoazo radicals D₁ are the radicals of formulae (10a), (10b), (10l), (11a), (11b) and (11f), especially (10l) and (11b).

In a preferred embodiment of the dyes according to the invention, D₁ as the radical of an azo dye is

a radical of formula (7) wherein

X₅ is fluorine or chlorine, especially chlorine,

R₈ is hydrogen or C₁-C₄alkyl, preferably hydrogen or methyl and especially hydrogen, and

G is a monoazo radical of the above-mentioned formula (10a), (10b), (10d) or (10e), especially (10a) or (10b), or D₁ as the radical of an azo dye is a radical of the above-mentioned formula (10a), (10b), (10l), (11a), (11b) or (11f), especially (10l) or (11b), wherein

the substituents (R₉)₀₋₃, (R₁₀)₀₋₃ and Z₁ have the definitions and preferred meanings given above.

As an aromatic tetraazo component, D₁ is, for example, phenylene or naphthylene unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino, sulfo, halogen or by carboxy, or a radical of formula (13)

wherein benzene rings I and II are unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino, sulfo, halogen or by carboxy and L is a direct bond or a C₁-C₁₀alkylene radical which may be interrupted by 1, 2 or 3 oxygen atoms, or L is a bridge member of formula

—CH═CH—, —N═N—, —NH—, —CO—, —NH—CO—, —NH—SO₂—, —NH—CO—NH—, —O—, —S— or —SO₂— and T₃ is halogen, e.g. chlorine or fluorine, preferably chlorine, or has the definitions and preferred meanings given above for T₁ as a non-fibre-reactive substituent.

L as a C₁-C₁₀alkylene radical, preferably a C₂-C₆alkylene radical, is straight-chain or branched or is a C₅-C₆cycloalkylene radical and preferably not interrupted by oxygen atoms.

L as a C₁-C₁₀alkylene radical is especially a C₂-C₄alkylene radical.

As an aromatic tetraazo component there also comes into consideration for D₁ a radical of formula (14)

D₁ as an aromatic tetraazo component is preferably a naphthylene substituted by from 1 to 3, preferably 2, sulfo groups, a radical of formula (13) wherein benzene rings I and II are unsubstituted or substituted by 1 or 2 substituents from the group sulfo, carboxy, methyl and methoxy and L is a direct bond, a C₂-C₄alkylene radical or a bridge member of formula —CH═CH—, —N═N—, —NH—, —CO—, —NH—CO—, —NH—SO₂—, —NH—CO—NH—, —O—, —S— or —SO₂—, especially a direct bond, a C₂-C₄alkylene radical or a bridge member of formula —CH═CH—, —N═N— or —NH—CO—; or D₁ is a radical of formula (14).

D₂ is, for example, phenyl or naphthyl unsubstituted or substituted by the fibre-reactive and non-fibre-reactive substituents mentioned above.

D₂ is preferably a radical of formula (15)

wherein

R₉ and Z₁ have the definitions and preferred meanings given above.

D₂ is especially a radical of formula (15a), (15b), (15c), (15d) or (15e)

wherein

(R₉)₀₋₂ denotes from 0 to 2 identical or different substituents selected from the group halogen, C₁-C₄alkyl, C₁-C₄alkoxy and sulfo, especially methyl, methoxy and sulfo,

Y₁ is a group —CH(Br)—CH₂—Br or —C(Br)═CH₂,

Y is vinyl, β-chloroethyl or β-sulfatoethyl,

k is the number 2 or 3, especially 2, and

l is the number 3 or 4, especially 3.

The numbers in the radicals of formulae (15a), (15c), (15d) and (15e) indicate possible bonding positions for the fibre-reactive radical.

D₂ is very especially a radical of formula (15a), (15b), (15c) or (15d), especially (15a) or (15b), the radicals of formulae (15a) and (15b) preferably each containing a fibre-reactive radical.

A radical of formula (15a) is a very important meaning of D₂, the radical of formula (15a) preferably containing a fibre-reactive radical.

The present invention relates also to a process for the preparation of the reactive dyes according to the invention, in which process

(i) approximately one molar equivalent of a diazotised amine of formula (16)

D₁—NH₂  (16)

is coupled to approximately one molar equivalent of a compound of formula (17)

or

(ii) approximately one molar equivalent of a tetraazotised diamine of formula (18)

H₂N—D₁—NH₂  (18)

is coupled to approximately two molar equivalents of a compound of formula (17), A, D₁ and m having the definitions and preferred meanings given above.

In the case of reaction (i), a reactive dye of formula (1) wherein b is the number 1 is obtained.

In the case of reaction (ii), a reactive dye of formula (1) wherein b is the number 2 is obtained. It may also be possible to use a mixture of two different compounds of formula (17), for example a 1:1 mixture, which differ from one another in the number m, the position of the radical A or the position of the sulfo group.

The diazotisation of the amines of formula (16) or the tetraazotisation of the diamines of formula (18) is carried out, for example, with a nitrite, e.g. with an alkali metal nitrite, such as sodium nitrite, in an acidic medium, e.g. in a hydrochloric-acid-containing medium, at temperatures of, for example, from −5 to 40° C. and preferably from −5 to 25° C.

The coupling to the coupling component of formula (17) is effected in a manner known per se at acidic or neutral to weakly alkaline pH values, for example at a pH value of from 1 to 10, and at temperatures of, for example, from −5 to 60° C., preferably from 0 to 30° C.

Compounds of formula (16) wherein D₁ is a radical of formula (4) and the compounds of formula (17) wherein A is a radical of formula (2) are described, for example, in GB-A-1 155 149.

The compound of formula (17) wherein A is a radical of formula (3) can be prepared, for example, by condensing approximately one molar equivalent of a compound of formula (19)

and approximately one molar equivalent of a compound of formula (20)

with approximately one molar equivalent of a compound of formula (21)

stepwise in any order,

D₂, R₁, R₂, X₁, m and n each being as defined above.

The condensation reactions between the compounds of formulae (19), (20) and (21) are generally carried out analogously to known processes, generally in aqueous solution at temperatures of, for example, from 0 to 50° C. and a pH value of, for example, from 4 to 10.

Preferably, in a first condensation step a compound of formula (19) is reacted with a compound of formula (21) and then, in a second condensation step, the resulting intermediate is reacted with a compound of formula (20). Instead of the compound of formula (19) it is also possible to use in the process the corresponding precursor of formula (22)

and to introduce the radical D₂ only after the first condensation step by means of a corresponding diazotisation and coupling reaction. The most important process variants are described in the Examples.

The compounds of formulae (16), (18), (19), (20), (21) and (22) are known or can be obtained in a manner known per se.

The reactive dyes according to the invention are suitable for dyeing and printing a wide variety of materials, especially hydroxyl-group-containing or nitrogen-containing fibre materials and also paper and leather. Examples include silk, wool, polyamide fibres and polyurethanes, and especially all types of cellulosic fibre materials. Such fibre materials are, for example, natural cellulose fibres, such as cotton, linen and hemp, and cellulose and regenerated cellulose. The dyes according to the invention are also suitable for dyeing or printing hydroxyl-group-containing fibres present in blend fabrics, for example blends of cotton and polyester fibres or polyamide fibres.

The present invention relates also to the use of compounds of formula (1) in the dyeing or printing of hydroxyl-group-containing or nitrogen-containing, especially cotton-containing, fibre materials.

The reactive dyes according to the invention can be applied to the fibre material and fixed to the fibre in a variety of ways, especially in the form of an aqueous dye solution or dye print paste. They are suitable both for the exhaust process and for dyeing in accordance with the pad-dyeing process; they can be used at low dyeing temperatures and require only short steaming times in the pad-steam process. The degrees of fixing are high and unfixed dye can be washed off readily, the difference between the degree of exhaust and the degree of fixing being remarkably small, that is to say the soaping loss is very small. The reactive dyes according to the invention are also suitable for printing, especially on cotton, and also for printing nitrogen-containing fibres, for example wool or silk or blend fabrics that contain wool.

The dyeings and prints produced using the reactive dyes according to the invention have a high tinctorial strength, a high colour brilliance and a high fibre-dye binding stability in both the acidic and the alkaline range. Special mention should be made of their good fastness to light and their good wet-fastness properties, such as fastness to washing, to water, to sea-water, to cross-dyeing and to perspiration. The dyeings obtained exhibit fibre levelness and surface levelness.

The present invention relates also to aqueous inks comprising a reactive dye of formula (1), A, D₁, b and m having the definitions and preferred meanings given above.

The dyes used in the inks should preferably have a low salt content, that is to say they should have a total content of salts of less than 0.5% by weight, based on the weight of the dyes. Dyes that have relatively high salt contents as a result of their preparation and/or as a result of the subsequent addition of diluents can be desalted, for example, by membrane separation procedures, such as ultrafiltration, reverse osmosis or dialysis.

The inks preferably have a total content of dyes of from 1 to 35% by weight, especially from 1 to 30% by weight and preferably from 1 to 20% by weight, based on the total weight of the ink. As a lower limit, a limit of 1.5% by weight, preferably 2% by weight and especially 3% by weight, is preferred.

The inks may comprise water-miscible organic solvents, for example C₁-C₄alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol and iso-butanol; amides, e.g. dimethylformamide and dimethylacetamide; ketones or ketone alcohols, e.g. acetone and diacetone alcohol; ethers, e.g. tetrahydrofuran and dioxane; nitrogen-containing heterocyclic compounds, e.g. N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidone; polyalkylene glycols, e.g. polyethylene glycol and polypropylene glycol; C₂-C₆-alkylene glycols and thioglycols, e.g. ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, thiodiglycol, hexylene glycol and diethylene glycol; further polyols, e.g. glycerol and 1,2,6-hexanetriol; and C₁-C₄alkyl ethers of polyhydric alcohols, e.g. 2-methoxy-ethanol, 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, 2-[2-(2-methoxyethoxy)-ethoxy]-ethanol and 2-[2-(2-ethoxyethoxy)ethoxy]ethanol; preferably N-methyl-2-pyrrolidone, diethylene glycol, glycerol or especially 1,2-propylene glycol, usually in an amount of from 2 to 30% by weight, especially from 5 to 30 % by weight and preferably from 10to 25% by weight, based on the total weight of the ink.

The inks may also comprise solubilisers, e.g. ε-caprolactam.

The inks may comprise thickeners of natural or synthetic origin inter alia for the purpose of adjusting the viscosity.

Examples of thickeners that may be mentioned include commercially available alginate thickeners, starch ethers or locust bean flour ethers, especially sodium alginate on its own or in admixture with modified cellulose, e.g. methylcellulose, ethylcellulose, carboxymethyl cellulose, hydroxyethylcellulose, methylhydroxyethylcellulose, hydroxypropyl cellulose or hydroxypropyl methylcellulose, especially with preferably from 20 to 25% by weight carboxymethylcellulose. Synthetic thickeners that may be mentioned are, for example, those based on poly(meth)acrylic acids or poly(meth)acrylamides.

The inks comprise such thickeners, for example, in an amount of from 0.01 to 2% by weight, especially from 0.01 to 1% by weight and preferably from 0.01 to 0.5% by weight, based on the total weight of the ink.

The inks may also comprise buffer substances, e.g. borax, borates, phosphates, poly-phosphates or citrates. Examples that may be mentioned include borax, sodium borate, sodium tetraborate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium tripolyphosphate, sodium pentapolyphosphate and sodium citrate. They are used especially in amounts of from 0.1 to 3% by weight, preferably from 0.1 to 1% by weight, based on the total weight of the ink, in order to establish a pH value of, for example, from 4 to 9, especially from 5 to 8.5.

As further additives, the inks may comprise surfactants or humectants.

Suitable surfactants include commercially available anionic or non-ionic surfactants. As humectants in the inks according to the invention there come into consideration, for example, urea or a mixture of sodium lactate (advantageously in the form of a 50% to 60% aqueous solution) and glycerol and/or propylene glycol in amounts of preferably from 0.1 to 30% by weight, especially from 2 to 30% by weight.

Preference is given to inks having a viscosity of from 1 to 40 mPa·s, especially from 1 to 20 mPa·s and preferably from 1 to 10 mPa·s.

The inks may-also comprise customary additives, such as antifoam agents or especially substances that inhibit the growth of fungi and/or bacteria. Such additives are usually used in amounts of from 0.01 to 1% by weight, based on the total weight of the ink.

The inks can be prepared in customary manner by mixing the individual constituents together in the desired amount of water.

The inks according to the invention are especially suitable for use in recording systems of the type in which an ink is expressed in the form of droplets from a small aperture, the droplets being directed onto a substrate on which an image is produced. Suitable substrates are, for example, paper, textile fibre materials or plastics films. Suitable recording systems are, for example, commercially available ink-jet printers for use in paper or textile printing, or writing implements, such as fountain pens or ballpoint pens, especially ink-jet printers.

Depending upon the nature of the use it may be necessary, for example, to adjust as necessary the viscosity or other physical properties of the ink, especially those properties which have an effect upon the affinity for the substrate in question.

Examples of paper that can be printed using the inks according to the invention include commercially available ink-jet paper, photographic paper, glossy paper and plastics-coated paper, e.g. Epson ink-jet paper, Epson photo paper, Epson glossy paper, Epson glossy film, HP special ink-jet paper, Encad photo gloss paper and IIford photo paper. Plastics films that can be printed using the inks according to the invention are, for example, transparent or milky/opaque. Suitable plastics films are, for example, 3M transparency film.

Textile fibre materials that come into consideration are, for example, nitrogen-containing or hydroxy-group-containing fibre materials, e.g. textile fibre materials of cellulose, silk, wool or synthetic polyamides, preferably cellulose.

The present invention accordingly also relates to a method of printing textile fibre materials, paper or plastics films, especially textile fibre materials or paper, more especially textile fibre materials, in accordance with the ink-jet printing method, which comprises using an aqueous ink comprising a reactive dye of formula (1), wherein A, D₁, b and m have the definitions and preferred meanings given above.

In ink-jet printing, individual droplets of the ink are sprayed onto a substrate in a controlled manner from a nozzle. For this purpose, predominantly the continuous ink-jet method and the drop-on-demand method are used. In the continuous ink-jet method, the droplets are produced continuously and any droplets not required for the printing are conveyed to a collecting vessel and recycled, whereas in the drop-on-demand method droplets are produced and printed as required; that is to say droplets are produced only when required for the printing. The production of the droplets can be effected, for example, by means of a piezo-inkjet head or by means of thermal energy (bubble jet). For the process according to the invention, printing by means of a piezo-inkjet head is preferred. Also preferred for the process according to the invention is printing in accordance with the continuous ink-jet method.

The recordings, for example prints, produced are distinguished especially by a high tinctorial strength and a high colour brilliance as well as by good light-fastness and wet-fastness properties.

The following Examples serve to illustrate the invention. Unless otherwise indicated, the temperatures are given in degrees Celsius, parts are parts by weight and percentages relate to percent by weight. Parts by weight relate to parts by volume in a ratio of kilograms to liters.

EXAMPLE 1

25.6 parts of 1,3-phenylenediamine-4-sulfonic acid are dissolved neutrally in 200 parts of water, and 4.6 parts of sodium acetate are added. At 1000° C. with vigorous stirring, 31 parts of γ-(β-chloroethylsulfonyl)butyryl chloride are added to the resulting solution, the pH of the reaction mixture being maintained at 5 by the simultaneous addition of an aqueous sodium hydroxide solution. The pH of the reaction mixture is then adjusted to 1.8, and the resulting precipitate is filtered off and dried, yielding 38.5 parts of an amine of formula D₁₀—NH₂ wherein D₁₀ corresponds to a radical of formula

EXAMPLE 2

38.5 parts of an amine of formula D₁₀—NH₂ according to Example 1 are dissolved neutrally in 400 parts of water, and 25 parts of a 4N sodium nitrite solution are added. The resulting solution is added dropwise at from 0 to 3° C. to a mixture of ice and 25 parts of concentrated hydrochloric acid. The mixture is stirred at that temperature for 1 hour.

EXAMPLE 3

26.7 parts of an amine of formula D₁₁—NH₂ wherein D₁₁ is a radical of formula

are introduced into 100 parts of water and stirred thoroughly. At 10° C., there are added to the resulting suspension first 24 parts of a 4N sodium nitrite solution and then 43 parts of a 31% naphthalenesulfonic acid solution The mixture is then stirred at from 15 to 20° C. for 3 hours.

EXAMPLES 4 to 29

Analogously to the procedure described in Example 2 or 3 it is possible to prepare the diazo compounds of the amines listed in Table 1 by using instead of the amine of formula D₁₀—NH₂ or D₁₁—NH₂ mentioned in Example 2 or 3 an equimolar amount of an amine of formula D_(xy)—NH₂ mentioned in Table 1.

TABLE 1 Amine Ex. D_(xy)-NH₂ D_(xy) 4 D₁₂-NH₂

5 D₁₃-NH₂

6 D₁₄-NH₂

7 D₁₅-NH₂

8 D₁₆-NH₂

9 D₁₇NH₂

10 D₁₈-NH₂

11 D₁₉-NH₂

12 D₂₀-NH₂

13 D₂₁-NH₂

14 D₂₂-NH₂

15 D₂₃-NH₂

16 D₂₄-NH₂

17 D₂₅-NH₂

18 D₂₆-NH₂

19 D₂₇-NH₂

20 D₂₈-NH₂

21 D₂₉-NH₂

22 D₃₀-NH₂

23 D₃₁-NH₂

24 D₃₂-NH₂

25 D₃₃-NH₂

26 D_(34a)-NH₂ to D_(34q)-NH₂

T₃₄: 26a D_(34a)-NH₂

26b D_(34b)-NH₂

26c D_(34c)-NH₂

26d D_(34d)-NH₂

26e D_(34e)-NH₂ T_(34e) = —NHCH₂CH₂OH 26f D_(34f)-NH₂ T_(34f) = —N(CH₂CH₂OH)₂ 26g D_(34g)-NH₂

26h D_(34h)-NH₂

26i D_(34i)-NH₂ T_(34i) = —NH—(CH₂)₂—O—(CH₂)₂—OH 26j D_(34j)-NH₂ T_(34j) =—NHCH₂CH₂SO₃H 26k D_(34k)-NH₂

26l D_(34l)-NH₂

26m D_(34m)-NH₂ T_(34m) = —NH—(CH₂)_(2—SO) ₂—(CH₂)₂—Cl 26n D_(34n)-NH₂ T_(34n) = —NH—(CH₂)₂—O—(CH₂)₂—SO₂—(CH₂)₂—Cl 26o D_(34o)-NH₂

26p D_(34p)-NH₂

26q D_(34q)-NH₂

27 D₃₅-NH₂

28 D₃₆—NH₂

29 D₃₇—NH₂

EXAMPLE 30

a) 19 parts of cyanuric chloride are dispersed in 75 parts of ice and 75 parts of water with addition of a wetting agent. A neutral solution of 31.9 parts of 1-amino-8-naphthol-3,6-disulfonic acid in 350 parts of water is added to the resulting dispersion. After several hours the pH of the reaction mixture is adjusted to from 4 to 5 by the addition of an aqueous sodium hydroxide solution.

b) The diazo compound obtained according to Example 3 is coupled at pH 4 to 5 to the densate contained in the reaction mixture according to a).

c) 27.1 parts of 1-amino-8-naphthol-3,6-disulfonic acid are added, in portions at 10° C., to the resulting solution according to b), the pH of the reaction mixture being maintained at 4 by the simultaneous addition of an aqueous sodium hydroxide solution. After about 1 hour, the pH of the reaction mixture is adjusted gradually to 6 by the addition of an aqueous sodium hydroxide solution, and the reaction mixture is heated to 20° C. and stirred to complete the reaction.

d) The suspension of the diazo compound according to Example 2 is added at 10° C. and pH 7 to 7.5 to the solution obtained according to c). To complete the reaction, the mixture is stirred for one hour at 25° C. and pH 7.5. The resulting solution is then clarified by filtration, freed of salt by dialysis and freeze-dried, yielding 140 parts of a compound which in the form of the free acid corresponds to formula (101)

and dyes cotton and wool a red shade having good allround properties.

EXAMPLES 31 to 73

Following the procedure as described in Example 30, but using instead of the diazo compound according to Example 3 an equimolar amount of a diazo compound according to one of Examples 2 and 4 to 33, there is obtained a compound which in the form of the free acid corresponds to formula

wherein D_(xy) is one of the radicals listed in Table 2, those radicals having the definitions given in example 2 and Table 1. The dyes dye cotton and wool the shade indicated in each case, which have good allround properties.

TABLE 2 Ex. D_(xy) Shade 31 D₁₀ red 32 D₁₂ red 33 D₁₃ red 34 D₁₄ red 35 D₁₅ red 36 D₁₆ red 37 D₁₇ red 38 D₁₈ red 39 D₁₉ red 40 D₂₀ red 41 D₂₁ red 42 D₂₂ red 43 D₂₃ red 44 D₂₄ red 45 D₂₅ red 46 D₂₆ red 47 D₂₇ red 48 D₂₈ red 49 D₂₉ red 50 D₃₀ red 51 D₃₁ red 52 D₃₂ red 53 D₃₃ red 54 D_(34a) red 55 D_(34b) red 56 D_(34c) red 57 D_(34d) red 58 D_(34e) red 59 D_(34f) red 60 D_(34g) red 61 D_(34h) red 62 D_(34i) red 63 D_(34j) red 64 D_(34k) red 65 D_(34l) red 66 D_(34m) red 67 D_(34n) red 68 D_(34o) red 69 D_(34p) red 70 D_(34q) red 71 D₃₅ red 72 D₃₆ red 73 D₃₇ red

EXAMPLE 74

Following the procedure as described in Example 30, but using instead of 27.1 parts of 1-amino-8-naphthol-3,6-disulfonic acid in step c) an equimolar amount of 2-amino-5-naphthol-7-sulfonic acid, there is obtained a compound which in the form of the free acid corresponds to formula (102)

and dyes cotton and wool a red shade having good allround properties.

EXAMPLE 75

Following the procedure as described in Example 30, but using instead of 31.9 parts of 1-amino-8-naphthol-3,6-disulfonic acid in step a) an equimolar amount of 2-N-methylamino-5-naphthol-7-sulfonic acid, there is obtained a compound which in the form of the free acid corresponds to formula (103)

and dyes cotton and wool a red shade having good allround properties.

EXAMPLE 76

Following the procedure as described in Example 30, but using instead of the diazo compound according to Example 2 in step d) an equimolar amount of the diazo compound according to Example 24, there is obtained a compound which in the form of the free acid corresponds to formula (104)

and dyes cotton and wool a red shade having good allround properties.

EXAMPLE 77

Following the procedure as described in Example 30, but using instead of 31.9 parts of 1-amino-8-naphthol-3,6-disulfonic acid in step a) an equimolar amount of 2-N-methylamino-5-naphthol-7-sulfonic acid and instead of the diazo compound according to Example 2 in step d) an equimolar amount of the diazo compound according to Example 24, there is obtained a compound which in the form of the free acid corresponds to formula (105)

and dyes cotton and wool a red shade having good allround properties.

EXAMPLE 78

a) 12.2 parts of an amine of formula D₃₈—NH₂ wherein D₃₈ is a radical of formula

are dissolved in 180 parts of water. To the resulting solution there are added at 25° C. first 5 parts of a 4N sodium nitrite solution and then 16 parts of a 31% naphthalenesulfonic acid solution. The mixture is then stirred for several hours at 25° C. to complete the reaction.

b) A solution of 10.3 parts of 1-[γ-(β-chloroethylsulfonyl)butyrylamino]-8-naphthol-3,6-disulfonic acid in 50 parts of water is added to the solution of the diazo compound obtained according to a), the pH of the reaction mixture being adjusted first to 6 with sodium hydrogen carbonate and then to 8 with sodium carbonate. When the reaction is complete, the pH is adjusted to 6 with dilute hydrochloric acid, the product is precipitated by the addition of potassium chloride and the precipitate is filtered and washed. For further purification, the precipitate is dissolved in water and precipitated by the addition of acetone. The precipitate is washed with acetone and dried, yielding 15.4 parts of a compound which in the form of the free acid corresponds to formula (106)

and dyes cotton and wool a red shade having good allround properties.

EXAMPLES 79 to 111

Following the procedure as described in Example 78, but using instead of 12.2 parts of an amine of formula D₃₈—NH₂ an equimolar amount of an amine of formula D_(xy)—NH₂, there is obtained a compound which in the form of the free acid corresponds to formula

wherein D_(xy) corresponds to one of the radicals listed in Table 3. The dyes dye cotton and wool the shade indicated in each case, which have good allround fastness properties.

TABLE 3 Amine Ex. D_(xy)-NH₂ Shade D_(xy) 79 D₃₉-NH₂

dark violet 80 D₄₀NH₂

dark blue 81 D₄₁-NH₂

navy 82 D₄₂-NH₂

navy 83 D₄₃-NH₂

dark blue 84 D₄₄-NH₂

blue 85 D₄₅-NH₂

blue 86 D₄₆-NH₂

violet 87 D₄₇-NH₂

red 88 D₄₈-NH₂

red D₄₉-NH₂ to D₇₀-NH₂

T_(xy): 89 D₄₉-NH₂

red 90 D₅₀-NH₂

red 91 D₅₁-NH₂

red 92 D₅₂-NH₂

red 93 D₅₃-NH₂

red 94 D₅₄-NH₂

red 95 D₅₅-NH₂

red 96 D₅₆-NH₂

red 97 D₅₇-NH₂

red 98 D₅₈-NH₂

red 99 D₅₉-NH₂

red 100 D₆₀-NH₂

red 101 D₆₁-NH₂

red 102 D₆₂-NH₂

red 103 D₆₃-NH₂

red 104 D₆₄-NH₂

red 105 D₆₅-NH₂

red 106 D₆₆-NH₂

red 107 D₆₇-NH₂

red 108 D₆₈-NH₂

red 109 D₆₉-NH₂

red 110 D₇₀-NH₂

red 111 D₇₁-NH₂

red

EXAMPLE 112

Following the procedure as described in Example 78, but using instead of 10.3 parts of 1-[γ-(β-chloroethylsulfonyl)butyrylamino]-8-naphthol-3,6-disulfonic acid an equimolar amount of 2-[γ-(β-chloroethylsulfonyl)butyrylamino]-5-naphthol-1,7-disulfonic acid, there is obtained a compound which in the form of the free acid corresponds to formula (107)

and dyes cotton and wool a red shade having good allround properties.

EXAMPLE 113

Following the procedure as described in Example 78, but using instead of 12.2 parts of an amine of formula D₃₈—NH₂ an equimolar amount of an amine of formula D₅₀—NH₂ and instead of 10.3 parts of 1-[γ-(β-chloroethylsulfonyl)butyrylamino]-8-naphthol-3,6-disulfonic acid an equimolar amount of 2-[γ-(β-chloroethylsulfonyl)butyrylamino]-5-naphthol-1,7-disulfonic acid, there is obtained a compound which in the form of the free acid corresponds to formula (108)

and dyes cotton and wool a red shade having good allround properties.

EXAMPLES 114 to 117

Likewise analogously to the procedure described in Example 78 it is possible to prepare the compounds which in the form of the free acid correspond to formulae (109) to (112) and dye cotton and wool the shades indicated, which have good allround properties.

EXAMPLE 118

a) 7.3 parts of a diamine of formula H₂N—D₇₂—NH₂ wherein D₇₂ is a radical of formula

are dissolved in 450 parts of water. 12.5 parts of a 4N sodium nitrite solution are then added to the resulting solution, and the solution so obtained is then added dropwise at from 5 to 10° C. to a mixture of 40 parts of a 31% naphthalenesulfonic acid solution and 50 parts of ice. The mixture is stirred for several hours at from 0 to 10° C. to complete the reaction.

b) 25.8 parts of 1-[γ-(β-chloroethylsulfonyl)butyrylamino]-8-naphthol-3,6-disulfonic acid are added in portions to the suspension of the tetraazo compound obtained according to a), the pH of the reaction mixture being adjusted first to 6.4 with sodium hydrogen carbonate and then to 8.5 with sodium carbonate. When the reaction is complete, the pH is adjusted to 6 with dilute hydrochloric acid and the product is precipitated by the addition of acetone and potassium chloride; the precipitate is filtered, washed with acetone and dried, yielding 14.6 parts of a compound which in the form of the free acid corresponds to formula (113)

and dyes cotton and wool a blue shade having good allround properties.

EXAMPLES 119 to 129

Following the procedure as described in Example 118, but using instead of 7.3 parts of a diamine of formula H₂N—D₇₂—NH₂ an equimolar amount of a diamine of formula H₂N—D_(xy)—NH₂, there is obtained a compound which in the form of the free acid corresponds to the following formula

wherein D_(xy) is a radical listed in Table 4. The dyes dye cotton and wool the shade indicated in each case, which have good allround properties.

TABLE 4 Diamine Ex. H₂N-D_(xy)-NH₂ D_(xy) Shade 119 H₂N-D₇₃-NH₂

red 120 H₂N-D₇₄-NH₂

blue 121 H₂N-D₇₅-NH₂

blue 122 H₂N-D₇₆-NH₂

blue 123 H₂N-D₇₇-NH₂

red 124 H₂N-D₇₈-NH₂

red 125 H₂N-D₇₉-NH₂

magenta 126 H₂N-D₈₀-NH₂

blue 127 H₂N-D₈₁-NH₂

blue 128 H₂N-D₈₂-NH₂

red 129 H₂N-D₈₃-NH₂

red

EXAMPLE 130

Following the procedure as described in Example 118, but using instead of 25.8 parts of 1-[γ-(β-chloroethylsulfonyl)butyrylamino]-8-naphthol-3,6disulfonic acid an equi-molar amount of 2-[γ-(β-chloroethylsulfonyl)butyrylamino]-5-naphthol-1,7-disulfonic acid, there is obtained a compound which in the form of the free acid corresponds to formula (114)

and dyes cotton and wool a violet shade having good allround properties.

EXAMPLE 131

Following the procedure as described in Example 118, but using instead of 7.3 parts of a diamine of formula H₂N—D₇₂—NH₂ an equimolar amount of a diamine of formula H₂N—D₇₄—NH₂ and instead of 25.8 parts of 1-[γ-(β-chloroethylsulfonyl)butyrylamino]-8-naphthol-3,6-disulfonic acid an equimolar amount of 2-[γ-(β-chloroethylsulfonyl)butrylamino]-5-naphthol-1,7-disulfonic acid, there is obtained a compound which in the form of the free acid corresponds to formula (115)

and dyes cotton and wool a violet shade having good allround properties.

EXAMPLES 132 and 133

Likewise analogously to the procedure described in Example 118 it is possible to prepare the compounds which in the form of the free acid correspond to formulae (116) and (117) and dye cotton and wool the shades indicated, which have good allround properties.

Dyeing Procedure I

100 parts of cotton fabric are placed at 60° C. in 1500 parts of a dyebath containing 45 g/l of sodium chloride and 2 parts of the reactive dye obtained according to Example 30. After 45 minutes at 60° C., 20 g/l of calcined soda are added. Dyeing is continued at that temperature for a further 45 minutes. The dyed goods are then rinsed, soaped at the boil for a quarter of an hour with a non-ionic detergent, rinsed again and dried.

As an alternative to that procedure, dyeing can be carried out at 80° C. instead of at 60° C.

Dyeing Procedure II

0.1 part of the dye according to Example 30 is dissolved in 200 parts of water, and 0.5 part of sodium sulfate, 0.1 part of a leveling agent (based on the condensation product of a higher aliphatic amine and ethylene oxide) and 0.5 part of sodium acetate are added. The pH is adjusted to a value of 5.5 with acetic acid (80%). The dyebath is heated at 50° C. for 10 minutes and then 10 parts of a woollen fabric are added. The dyebath is heated to a temperature of 100° C. in the course of about 50 minutes and dyeing is carried out at that temperature for 60 minutes. The dyebath is then cooled to 90° C. and the dyed goods are removed. The woollen fabric is washed with hot and cold water, then spun and dried.

Printing Procedure

While stirring rapidly, 3 parts of the dye obtained according to Example 30 are sprinkled into 100 parts of a stock thickener containing 50 parts of 5% sodium alginate thickener, 27.8 parts of water, 20 parts of urea, 1 part of sodium m-nitrobenzenesulfonate and 1.2 parts of sodium hydrogen carbonate. The print paste so obtained is used to print a cotton fabric; drying is carried out and the resulting printed fabric is steamed in saturated steam at 102° C. for 2 minutes. The printed fabric is then rinsed, if desired soaped at the boil and again rinsed, and then dried. 

What is claimed is:
 1. A reactive dye of the formula (1a)

wherein b is the number 2, D₁ is phenylene or naphthylene unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino, sulfo, halogen or by carboxy, or a radical of formula (13)

wherein benzene rings I and II are unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino, sulfo, halogen or by carboxy and L is a C₁-C₁₀alkylene radical which may be interrupted by 1, 2 or 3 oxygen atoms, or L is a bridge member of the formula

—CH═CH—, —N═N—, —NH—, —CO—, —NH—CO—, —NH—SO₂—, —NH—CO—NH—, —O—, —S— or —SO₂— and T₃ is halogen, or a non-fibre-reactive substituent, or D₁ is a radical of the formula (14)

wherein R₁ is hydrogen or C₁-C₄alkyl, Y is vinyl or a radical —CH₂—CH₂-U and U is a group removable under alkaline conditions, I is the number 2, 3, 4, 5 or 6, and m is the number 0 or
 1. 2. A reactive dye according to claim 1, wherein D₁ is a naphthylene substituted by from 1 to 3 sulfo groups, or a radical of the formula (13), wherein benzene rings I and II are unsubstituted or substituted by 1 or 2 substituents selected from the group consisting of sulfo, carboxy, methyl and methoxy and L is a C₂-C₄alkylene radical or a bridge member of the formula —CH═CH—, —N═N—, —NH—, —CO—, —NH—CO—, —NH—SO₂—, —NH—CO—NH—, —O—, —S— or —SO₂—, or D₁is a radical of the formula (14).
 3. A process for dyeing or printing hydroxyl-group-containing or nitrogen-containing fibre materials, which comprises applying to said fibre materials a reactive dye according to claim
 1. 4. A process according to claim 3, wherein said fibre material is cellulosic fibre material.
 5. A process according to claim 3, wherein said fibre material is cotton.
 6. An aqueous ink comprising a reactive dye of formula (1a) according to claim 1 and an aqueous carrier.
 7. A process for printing textile fibre materials, paper or plastics films in accordance with the ink-jet printing method, which comprises applying to said materials an aqueous ink according to claim
 6. 